EP3008145B1 - Composition de matériau de revêtement, et films revêtus obtenus par leur revêtement - Google Patents

Composition de matériau de revêtement, et films revêtus obtenus par leur revêtement Download PDF

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Publication number
EP3008145B1
EP3008145B1 EP14720111.5A EP14720111A EP3008145B1 EP 3008145 B1 EP3008145 B1 EP 3008145B1 EP 14720111 A EP14720111 A EP 14720111A EP 3008145 B1 EP3008145 B1 EP 3008145B1
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EP
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Prior art keywords
coating material
resin
coated film
mass
material composition
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EP14720111.5A
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German (de)
English (en)
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EP3008145A1 (fr
EP3008145B8 (fr
Inventor
Takahiro Tsujita
Shinji Yagi
Nobuhiro NISHIDA
Yoshitomo Takeuchi
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Akzo Nobel Coatings International BV
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BASF Coatings GmbH
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Priority to PL14720111T priority Critical patent/PL3008145T3/pl
Publication of EP3008145A1 publication Critical patent/EP3008145A1/fr
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Publication of EP3008145B1 publication Critical patent/EP3008145B1/fr
Publication of EP3008145B8 publication Critical patent/EP3008145B8/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/58—Epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6212—Polymers of alkenylalcohols; Acetals thereof; Oxyalkylation products thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6407—Reaction products of epoxy resins with at least equivalent amounts of compounds containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4028—Isocyanates; Thioisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/69—Particle size larger than 1000 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres

Definitions

  • the present invention relates to a coating material composition which is outstanding, in particular, in its pressure mark resistance as a backcoat (underside) coating material in the production of precoated steel sheet.
  • precoated steel sheet is metal sheet (cut sheet or coil) which is subjected to coating beforehand prior to the fabrication thereof, and it is widely employed for building materials such as roofs and walls, and for the housings of audio equipment, refrigerators, and partitions, in that there are advantages in terms of cost, energy savings, and materials savings when compared to post-coating.
  • the coating of precoated steel sheet is generally carried out at both the upper and underside faces thereof, where the upper face side is the region forming the outer face of the product following fabrication, so there is applied thereto a coating material which is outstanding in terms of coated film external appearance, physical properties (hardness, adhesion, scratch resistance, and bendability), corrosion resistance, and weatherability, and the coating process adopted therefor is a 2-coat 2-bake system employing a primer and topcoat coating material, or a 3-coat 3-bake system employing a primer, intermediate-coat coating material, and a topcoat coating material.
  • the underside face is positioned on the inside of the product following fabrication, the same level of coated film external appearance and weatherability is not demanded as in the case of the upper face side, so, from the point of view of cost, the coating thereof is generally carried out by a 1-coat 1-bake system employing just a backcoat coating material, but in applications where corrosion resistance is especially demanded a 2-coat 2-bake system employing a primer and a backcoat coating material is adopted.
  • the upper and underside faces of the precoated steel ideally have the same appearance (gloss, color tone), since the underside of the precoated steel forms the inside of the processed product following fabrication it is hardly ever seen, so a high level of design is not demanded and usually just, for example, two types of coating material are provided as the backcoat coating material, namely a high-gloss backcoat coating material and a low-gloss backcoat coating material, such that in the case where the upper side gloss is comparatively high the high-gloss backcoat coating material is applied to the underside, whereas in the case where the upper side gloss is comparatively low the low-gloss backcoat coating material is applied to the underside, and, in this way, the number of coating material products employed is reduced and costs improved.
  • the low-gloss backcoat coating material has hitherto been produced by incorporating an inorganic powder such as silica which has a gloss-lowering effect, but problems have arisen such as a lowering in coatability caused by a rise in viscosity, or a reduction in bendability, and also gloss transfer due to poor pressure mark resistance.
  • gloss transfer due to poor pressure mark resistance refers to the phenomenon whereby, in the case where precoated steel sheet with a different gloss at the upper side from that at the underside has a coil shape, and strong pressure is applied while the upper side and underside are in contact, the gloss of the high-gloss face is lowered while, conversely, the gloss of the low-gloss face is raised, and this is perceived as an apparent transfer of gloss from the high-gloss side to the low-gloss side.
  • patent document 1 there is disclosed a backcoat coating material composition which contains at least one type of fine resin particles selected from polyamide resins, polyacrylonitrile resins, and acrylic resins.
  • Patent application FR 2 874 018 A1 discloses an aqueous paint composition comprising a water-soluble pure acrylic resin (A) as a binder resin and a polycarbodiimide compound (D) as a crosslinking agent; with the aqueous paint composition being characterized by further comprising acrylic resin beads (E) and urethane resin beads (F), wherein: in terms of solid component, the ratio of the water-soluble pure acrylic resin (A) relative to the binder resin, the ratios of the acrylic resin beads (E) and of the urethane resin beads (F) relative to the total of the binder resin and the crosslinking agent, and the equivalent ratio of the carbodiimide groups of the polycarbodiimide compound (D) relative to the carboxyl groups of the water-soluble pure acrylic resin (A) satisfy their respective specific ranges.
  • the objectives of the present invention are both to provide a coating material composition for forming on the underside of precoated steel sheet a coated film which, in particular, is outstanding in its pressure mark resistance, coated film adhesion, and bendability, and also to provide coated films obtained by the application of this coating material composition.
  • the present inventors have discovered that in the case where the compression strength of the resin beads at the time of the 10% pressurized deformation is restricted to a specified range and, furthermore, in the case where the recovery following the 90% pressurized deformation is restricted to a specified range, there is obtained a coating material composition which can form a backcoat film showing good evaluation results in terms of pressure mark resistance, coated film adhesion, and bendability, and the present invention has been perfected based on this discovery.
  • the present invention relates to a coating material composition which contains coated film forming resin (A), crosslinking agent (B), and resin beads (C), where the compression strength of said resin beads (C) at the time of the 10% pressurized deformation of an individual resin bead by means of a micro-compression tester lies between 0.1 MPa and 20 MPa and, furthermore, the recovery of the resin beads (C) following the 90% pressurized deformation of an individual resin bead by means of a micro-compression tester is at least 80%.
  • the present invention provides a coating material composition where, in the coating material composition described above, the content by mass of the aforesaid resin beads (C) lies between 0.5 and 20 mass% in terms of the total solids content by mass of aforesaid coated film forming resin (A) and aforesaid crosslinking agent (B).
  • the present invention provides a coating material composition where the compression strength at the time of the aforesaid 10% pressurized deformation lies between 0.2 MPa and 1.5 MPa and, furthermore, the content by mass of the aforesaid resin beads (C) lies between 0.8 and 15 mass% in terms of the total solids content by mass of aforesaid coated film forming resin (A) and aforesaid crosslinking agent (B).
  • the average particle diameter of (C) is preferably between 5 and 30 ⁇ m.
  • the present invention provides a coating material composition where, in the composition described above, the aforesaid resin beads (C) are produced by a urethane reaction.
  • the present invention also provides a coating material composition where the aforesaid resin beads (C) are produced by a urethane reaction, and the starting material isocyanate is difunctional.
  • coated films which are outstanding in terms of their pressure mark resistance, coated film adhesion, and bendability, by application of an inventive coating material composition.
  • the coating material composition of the present invention By application of the coating material composition of the present invention to the underside, it is possible to obtain a coated film which is outstanding in terms of pressure mark resistance, coated film adhesion, and bendability.
  • the coated film forming resin (A) employed in the coating material composition of the present invention is not particularly restricted providing it is a resin which has a coated film forming capacity and, furthermore, has functional groups which can react with crosslinking agent (B), but, in terms of bendabilyty and close adhesion, it is preferably at least one coated film forming resin selected from epoxy resins and polyester resins.
  • Such coated film forming resins can be employed on their own, or it is possible to use combinations of two or more types.
  • examples of the epoxy resin are bisphenol A type epoxy resins synthesized from bisphenol A and epichlorohydrin, and bisphenol F type epoxy resins synthesized from bisphenol F and epichlorohydrin, but the bisphenol A type epoxy resins are preferred in terms of corrosion resistance.
  • the number average molecular weight of the epoxy resin is preferably between 400 and 10,000, and preferably between 2,000 and 8,000.
  • the value of the number average molecular weight in this invention is that determined by means of gel permeation chromatography (GPC) using polystyrenes as standard materials.
  • epoxy resin is employed as the coated film forming resin (A)
  • all or some of the epoxy groups or hydroxyl groups in this epoxy resin may be modified by reaction with a modifier.
  • epoxy resin modifiers are polyesters, alkanolamines, caprolactone, isocyanate compounds, phosphoric acid compounds, and acid anhydrides. These modifiers may be employed on their own, or a combination of two or more types thereof can be used.
  • this polyester resin can be obtained by known methods employing a reaction between polyhydric alcohols and polybasic acids.
  • polyhydric alcohols examples include glycols, and trihydric or higher polyhydric alcohols.
  • glycols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, neopentyl glycol, hexylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-butyl-2-ethyl-1,3-propanediol, methylpropanediol, cyclohexanedimethanol, 3,3-diethyl-1,5-pentanediol, and the like.
  • trihydric or higher polyhydric alcohols examples include glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, and dipentaerythritol. These polyhydric alcohols can be used on their own, or it is possible to employ combinations of two or more thereof.
  • polycarboxylic acids are used as the polybasic acids but, where required, a monobasic fatty acid, may also be jointly employed.
  • the polycarboxylic acids include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, 4-methylhexahydrophthalic acid, bicyclo[2,2,1]heptane-2,3-dicarboxylic acid, trimellitic acid, adipic acid, sebacic acid, succinic acid, azelaic acid, fumaric acid, maleic acid, itaconic acid, pyromellitic acid, dimer acid, etc., and the anhydrides thereof, and also 1,4-cyclohexanedicarboxylic acid, isophthalic acid, tetrahydroisophthalic acid, hexahydroisophthalic acid, and hexahydroterephthalic acid.
  • These polybasic acids may be used on their own, or it is possible to employ combinations of two or more
  • the hydroxyl value of the polyester resin lies between 5 and 200 mgKOH/g.
  • the number average molecular weight of said polyester resin be from 500 to 20,000.
  • crosslinking agent (B) employed in the present invention reacts with coated film forming resin (A) to form a cured coated film.
  • crosslinking agent (B) include amino resins, polyisocyanate compounds, and blocked polyisocyanate compounds, but, from the point of view of bendability and general applicability, melamine resins and blocked polyisocyanate compounds are preferred. These crosslinking agents can be used on their own, or they can be employed in combinations of two or more thereof.
  • 'Amino resins' refers to the resins obtained by the addition to and condensation of formaldehyde with compounds which possess an amino group, specific examples of which are melamine resins, urea resins, and guanamine resins. Of these, the melamine resins are preferred.
  • the melamine resins include the partially- or wholly-methylolated melamine resins obtained by the reaction between melamine and formaldehyde, partial- or wholly-alkyl ether type melamine resins obtained by the partial or total etherification of the methylol groups in methylolated melamine resins using an alcohol component, imino group-containing melamine resins, and melamine resins comprising mixtures of these.
  • the alkyl ether type melamine resins include methylated melamine resins, butylated melamine resins, and methyl/butyl mixed-alkyl type melamine resins.
  • polyisocyanate compounds examples include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and other such aliphatic diisocyanates, isophorone diisocyanate, xylylene diisocyanate (XDI), m-xylylene diisocyanate, hydrogenated XDI, hydrogenated TDI, hydrogenated MDI, and other such alicyclic diisocyanates, tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), and other such aromatic diisocyanates, together with the adducts, biurets, and isocyanurates thereof.
  • These polyisocyanate compounds can be used on their own, or combinations of two or more thereof can be employed.
  • blocked polyisocyanate compounds are compounds where the isocyanate groups in a polyisocyanate compound are blocked with, for example, alcohols such as butanol, oximes such as methyl ethyl ketoxime, lactams such as ⁇ -caprolactam, diketones such as acetoacetic acid diesters, imidazoles such as imidazole per se or 2-ethylimidazole, and phenols such as m-cresol.
  • alcohols such as butanol
  • oximes such as methyl ethyl ketoxime
  • lactams such as ⁇ -caprolactam
  • diketones such as acetoacetic acid diesters
  • imidazoles such as imidazole per se or 2-ethylimidazole
  • phenols such as m-cresol.
  • the solids component content, by mass, of crosslinking agent (B) in terms of the coated film forming resin (A) in the coating material composition of the present invention be from 3 to 60 mass%. If it is less than 3 mass% the coated film strength may be lowered, whereas if it is more than 60 mass% the bendability may be lowered.
  • the various known components normally used in the coating materials field there may also be optionally included the various known components normally used in the coating materials field.
  • these are leveling agents, defoaming agents and other types of surface conditioners, dispersing agents, sedimentation preventives, UV absorbers, light stabilizers, and various other types of additives, coloring pigments, extender pigments, and various other types of pigments, glitter materials, curing catalysts, and organic solvents.
  • the resin beads (C) employed in the present invention have a compression strength at the time of the 10% pressurized deformation of an individual resin bead by means of a micro-compression tester of between 0.1 MPa and 20 MPa, preferably between 0.15 MPa and 10 MPa, and more preferably between 0.2 MPa and 1.5 MPa. Furthermore, the recovery of the resin beads (C) following 90% pressurized deformation of an individual resin bead by means of the micro-compression tester is at least 80%, and preferably at least 90%, and this contributes to the anti-blocking property of the cured coated film.
  • the compression strength of the resin beads (C) at the time of the 10% pressurized deformation of an individual resin bead in the present invention and the recovery thereof following 90% pressurized deformation are the values measured by means of a micro-compression tester ("MCT-510"®, produced by the Shimadzu Corporation). Specifically, a single bead is set on the lower pressure plate of the tester and, while lowering the upper pressure plate, the single bead is subjected to compressive deformation during which time measurement of the load is performed, and the load at the point when the resin bead diameter is reduced 10% is taken as the compression strength at the time of 10% pressurized deformation.
  • MCT-510® micro-compression tester
  • the content, by mass, of the resin beads (C) in terms of the total solids content by mass of aforesaid coated film forming resin (A) and aforesaid crosslinking agent (B) is preferably from 0.5 to 20 mass%, more preferably from 0.8 to 15 mass%, and still more preferably from 1.0 to 15 mass%. If it is less than 0.5 mass%, the pressure mark resistance may be lowered. On the other hand, there may be a reduction in bendability if it is more than 20 mass%.
  • the average particle diameter of the resin beads (C) is preferably 5-30 ⁇ m. If the average particle diameter is less than 5 ⁇ m, the enhancement in the pressure mark resistance of the coated film is insufficient, whereas if it exceeds 30 ⁇ m then, as well as the external appearance being unsatisfactory, there is also a lowering in the pressure mark resistance due to shedding of the resin beads.
  • the starting materials isocyanate and polyol are mixed together.
  • Di-functional or trifunctional isocyanate and the polyol are mixed together beforehand, in preparation for the subsequent suspension polymerization.
  • difunctional isocyanate and polyol are used, it is possible to obtain resin beads which are highly elastic.
  • trifunctional isocyanate and polyol are used, rigid resin beads are formed. Thus, these may be suitably employed together to adjust the properties.
  • isocyanate type there may be used a type which undergoes yellowing or a non-yellowing type.
  • the polyol employed is mixed with the isocyanate in equimolar proportions.
  • the proportions of isocyanate and polyol are altered according to the molecular weight of the polyol used. If there is too little polyol component, hard particles are obtained, whereas if there is too much polyol component soft particles tend to be obtained.
  • the polyol component may be a polyester-, polyether- or acrylic-polyol. Moreover, these can also be jointly employed.
  • a diluent solvent be mixed with the beads starting materials.
  • diluent solvents are those which dissolve the polyisocyanate prepolymer containing blocked isocyanate groups, and which do not inhibit the polymerization reaction.
  • the aforesaid beads starting material is added to water containing a suspension stabilizer.
  • This water containing a suspension stabilizer is prepared by dissolving or dispersing a suspension stabilizer in water.
  • the suspension stabilizer is not particularly restricted providing it is of a kind generally employed in suspension polymerizations, and it may be of an organic or inorganic type.
  • Specific examples of suspension stabilizers include methyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, and other types of cellulose-based water-soluble resins, polyvinyl alcohol, polyacrylates, polyethylene glycol, polyvinyl pyrrolidone, polyacrylamides, tertiary phosphates, and the like. One of these may be used on its own, or two or more may be employed together.
  • a surfactant may be jointly employed along with the suspension stabilizer.
  • the surfactant jointly employed along with the suspension stabilizer may be an anionic surfactant, cationic surfactant, nonionic surfactant, or amphoteric surfactant.
  • the amount of suspension stabilizer added per 100 parts by mass of the isocyanate prepolymer containing blocked isocyanate groups will differ according to the type employed, but from 1 to 10 parts by mass is preferred. When the added amount of suspension stabilizer lies within this range, the average particle diameter of the beads tends to fall within the range 5-30 ⁇ m which is suitable as a filler.
  • the amount of suspension stabilizer is greater than 10 parts by mass, the average particle diameter tends to be less than 5 ⁇ m and, furthermore, the viscosity of the suspension liquid tends to rise, so that the solid/liquid separation and washing steps become more difficult.
  • the particles tend to aggregate and, moreover, there is a tendency for the particle diameter to rise above 30 ⁇ m.
  • the amount of water in which the dispersion stabilizer has been dissolved or dispersed preferably lies in the range from 100 to 300 parts by mass per 100 parts by mass of the polyisocyanate prepolymer containing blocked isocyanate groups.
  • a stirring method is adopted to bring about dispersion thereof in particle form.
  • the stirring rate at this time is preferably suitably adjusted so that the urethane starting material prepared in the first stage adopts a specified particle diameter.
  • the temperature is raised to 30-90°C, and suspension polymerization carried out for between 1 and 6 hours so that a suspension liquid is obtained.
  • a means such as filtering or centrifuging is used for the solid/liquid separation in the after-treatment step.
  • the separated and recovered reactive polyurethane beads are further washed with water, so that any suspension stabilizer remaining on the polyurethane beads is removed.
  • a hot drying method there is employed a hot drying method, an airborne drying method, a vacuum drying method, an infrared drying method, or the like.
  • the drying temperature be set to between 40 and 110°C and that the drying time be from 2 to 40 hours.
  • the suspension liquid When subjecting the suspension liquid to solid/liquid separation and washing, the suspension liquid may also be treated with, for example, an enzyme such as a cellulose degrading enzyme or a polyvinyl alcohol degrading enzyme, or a reagent such as a hypochlorite, to decompose the suspension stabilizer.
  • an enzyme such as a cellulose degrading enzyme or a polyvinyl alcohol degrading enzyme
  • a reagent such as a hypochlorite
  • the materials which are coated using the coating material composition of the present invention there are hot-dip galvanized steel sheet, electro-galvanized steel sheet, alloyed galvanized steel sheet, aluminum-zinc coated steel sheet, nickel-zinc coated steel sheet, magnesium-aluminum-zinc coated steel sheet, magnesium-aluminum-silica-zinc coated steel sheet, and various other types of galvanized steel sheet, stainless steel sheet, and aluminum sheet, etc., which have undergone treatment with chrome-free or chromate-based chemical treatment agents.
  • a topcoat coating material is applied onto a coated film of primer.
  • a topcoat coating material By applying a topcoat coating material, it is possible to confer attractiveness on the precoated steel sheet, and it is also possible to enhance various properties demanded of the precoated steel sheet such as bendability, weatherability, chemical resistance, contamination resistance, water resistance, and corrosion resistance.
  • the uses of the coating material composition of the present invention are not particularly restricted, but it is preferably employed as the backcoat coating material in the production of precoated steel sheet.
  • coating method used for the coating material composition of the present invention it is possible to employ any of the methods normally used in the production of precoated steel sheet, for example roll coater coating, curtain flow coater coating, and the like.
  • the usual coating conditions in the production of precoated steel sheet can be employed as the coating conditions in the case of the coating material composition of the present invention.
  • the coated film thickness of primer coating material in the production of the precoated steel sheet is, for example, 1 to 30 ⁇ m, and the hot curing conditions for the primer coated film are, for example, a maximum attained sheet temperature of 150-300°C and a curing time of 15 to 150 seconds.
  • the coated film thickness of the topcoat coating material in the production of the precoated steel sheet is, for example, 10 to 25 ⁇ m, and the hot curing conditions for the topcoat coated film are, for example, a maximum attained sheet temperature of 190-250°C and a hardening time of 20 to 180 seconds.
  • the starting materials shown in Table 1 were introduced in the amounts shown in Table 1 into a 2 L flask equipped with a stirrer, and reaction then carried out for 4 hours at 80°C while stirring, to produce the urethane prepolymer.
  • the materials shown in Table 1 were introduced in the amounts shown in Table 1 into a separate 2 L flask equipped with a stirrer and then, while stirring, the urethane prepolymer prepared in the first flask was dispersed therein and reaction carried out for 2 hours at 60°C.
  • the resin beads obtained by means of the reaction were filtered off using a metal mesh and washed with pure water, after which drying was carried out for 3 hours in a hot-air dryer at 80°C and, in this way, resin beads C-1 to C-14, and RC-1 to RC-3, were obtained respectively.
  • the average particle diameter of the synthesized resin beads was measured using a laser diffraction type particle size distribution measurement device ("SALD-2300" ® , produced by the Shimadzu Corporation). The results are shown in Table 1.
  • epoxy resin commercial name "jER 1009” ®; a bisphenol A type epoxy resin, produced by the Mitsubishi Chemical Co.
  • 80 parts of epoxy resin commercial name "jER 1009” ®; a bisphenol A type epoxy resin, produced by the Mitsubishi Chemical Co.
  • crosslinking agent (B) 21 parts of a blocked polyisocyanate compound (commercial name "Desmodur BL-3175" ® , (solids content 75%), produced by the Sumika Bayer Urethane Co.) and 1.2 parts of dibutyltin dilaurate (DBTDL) were added to this mill base and uniform mixing performed, to obtain backcoat coating material base E-1 (solids content 51%).
  • DBTDL dibutyltin dilaurate
  • epoxy resin commercial name "jER1009” ® ; a bisphenol A type epoxy resin, produced by the Mitsubishi Chemical Co.
  • crosslinking agent (B) 21 parts of a blocked polyisocyanate compound (commercial name "Desmodur BL-3175" ® , produced by the Sumika Bayer Urethane Co.) and 1.2 parts of dibutyltin dilaurate (DBTDL) were added to this mill base and uniform mixing performed, to obtain primer coating material P-1.
  • DBTDL dibutyltin dilaurate
  • the resin beads (C) shown in Tables 2 and 3 were added in the amounts shown in Tables 2 and 3 to 400 parts of the backcoat coating material base E-1 obtained in Production Example 1, then fine silica powder (commercial name "Nipsil E-200A” ® , produced by the Tosoh Silica Corporation) added and adjustment performed such that the 60° mirror surface gloss was 10, and, in this way, backcoat coating materials CB-1 to CB-18 and RCB-1 to RCB-3 were obtained.
  • the combined total of coated film forming resin (A) and crosslinking agent (B) contained per 400 parts by mass of the backcoat coating material base E-1 was 100 parts by mass.
  • the resin beads (C) shown in Tables 4 and 5 were added in the amounts shown in Tables 4 and 5 to 327 parts of the backcoat coating material base E-2 obtained in Production Example 2, then fine silica powder (commercial name "Nipsil E-200A” ® , produced by the Tosoh Silica Corporation) added and adjustment performed such that the 60° mirror surface gloss was 10, and, in this way, backcoat coating materials CB-31 to CB-48, and RCB-31 to RCB-33, were obtained.
  • the combined total of coated film forming resin (A) and crosslinking agent (B) contained per 327 parts by mass of backcoat coating material base E-2 was 100 parts by mass.
  • backcoat coating materials CB-1 to CB-48, and RCB1 to RCB33 were respectively applied to one face of chemically-treated aluminum/zinc alloy coated steel sheets (Al 55%) of sheet thickness 0.35 mm, to give a dry film thickness of 8 ⁇ m, and then these sheets were each baked in a hot air dryer for 40 seconds at a maximum attained sheet temperature of 220°C, to form the backcoat coated film.
  • primer coating material P-1 was coated onto that surface of the chemically-treated aluminum/zinc alloy coated steel sheets (Al 55%) of sheet thickness 0.35 mm which had not been coated with the backcoat, to give a dry film thickness of 5 ⁇ m, and then the sheets each baked in a hot air dryer for 40 seconds at a maximum attained sheet temperature of 210°C, to form the primer coated film.
  • this primer coated film was coated with a polyester resin based topcoat coating material (commercial name "Precolor HD0030" ® ; produced by BASF Japan, brown color) to give a dry film thickness of 15 ⁇ m, and then the respective sheets baked in a hot air dryer for 40 seconds at a maximum attained sheet temperature of 220°C, to form the test pieces.
  • a polyester resin based topcoat coating material commercial name "Precolor HD0030” ® ; produced by BASF Japan, brown color
  • test pieces were cut of size 10 cm ⁇ 10 cm, then the front and back faces superimposed, and these left for 24 hours in a 50°C atmosphere in a state with a pressure of 5 MPa/cm 2 applied. Subsequently, the temperature was returned to room temperature and the pressure released, after which the superimposed test pieces were separated and observation performed of the surface pressure marks.
  • the test piece was bent over by 180° with sheets identical to the test piece interposed between.
  • the designation employed was 0T, 2T, etc., based on the number of sheets identical to the test piece interposed in this way.
  • 0T was the case where the test piece was bent over without a sheet identical to the test piece being interposed
  • 2T was the case where the test piece was bent over with two sheets identical to the test piece interposed.
  • the 2T and 3T tests were carried out and, after bending over in this way, cellophane tape was firmly affixed to the crown region, then the tape end suddenly peeled away at an angle of 45°, and the peeled state of the coated film evaluated as follows.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Nanotechnology (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)

Claims (7)

  1. Composition de matériau de revêtement qui contient une résine filmogène (A), un agent de réticulation (B) et des billes de résine (C), la résistance à la compression desdites billes de résine (C) au moment de la déformation sous pression de 10 % d'une bille de résine individuelle au moyen d'un appareil d'essai de microcompression se situant entre 0,1 MPa et 20 MPa et, en outre, la récupération des billes de résine (C) après la déformation sous pression de 90 % d'une bille de résine individuelle au moyen d'un appareil d'essai de microcompression étant d'au moins 80 %.
  2. Composition de matériau de revêtement selon la revendication 1 dans laquelle la teneur massique des billes de résine (C) se situe entre 0,5 et 20 % en masse, rapporté à la teneur massique totale en matières solides de la résine filmogène (A) et de l'agent de réticulation (B).
  3. Composition de matériau de revêtement selon la revendication 1 ou la revendication 2 dans laquelle le diamètre moyen de particules des billes de résine (C) se situe entre 5 et 30 µm.
  4. Composition de matériau de revêtement selon l'une quelconque des revendications 1 à 3 dans laquelle la résistance à la compression au moment de la déformation sous pression de 10 % se situe entre 0,2 MPa et 1,5 MPa et, en outre, la teneur massique des billes de résine (C) se situe entre 0,8 et 15 % en masse, rapporté à la teneur massique totale en matières solides de la résine filmogène (A) et de l'agent de réticulation (B).
  5. Composition de matériau de revêtement selon l'une quelconque des revendications 1 à 4 dans laquelle les billes de résine (C) sont produites par réaction d'un uréthane.
  6. Composition de matériau de revêtement selon l'une quelconque des revendications 1 à 5 dans laquelle les billes de résine (C) sont produites par réaction d'un uréthane et, en outre, l'isocyanate de départ est bifonctionnel.
  7. Films de revêtement obtenus par l'application de la composition de matériau de revêtement selon l'une quelconque des revendications 1 à 6.
EP14720111.5A 2013-06-13 2014-04-25 Composition de matériau de revêtement, et films revêtus obtenus par leur revêtement Active EP3008145B8 (fr)

Priority Applications (1)

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JP2013124787A JP6581330B2 (ja) 2013-06-13 2013-06-13 塗料組成物及びこれを塗装して得られる塗膜
PCT/EP2014/058481 WO2014198452A1 (fr) 2013-06-13 2014-04-25 Composition de matériau de revêtement, et films revêtus obtenus par leur revêtement

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EP (1) EP3008145B8 (fr)
JP (1) JP6581330B2 (fr)
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ES (1) ES2623278T3 (fr)
MX (1) MX2015017010A (fr)
PL (1) PL3008145T3 (fr)
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JP6700961B2 (ja) * 2016-05-13 2020-05-27 日鉄ステンレス株式会社 クリヤ塗装ステンレス鋼板
JP6992495B2 (ja) * 2017-12-25 2022-01-13 日本製鉄株式会社 塗装金属板およびこれを用いた外装建材

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DE19654296A1 (de) * 1996-12-27 1998-07-02 Bollig & Kemper Gmbh & Co Kg Beschichtung für ein elektrisch leitfähiges Substrat
JPWO2005113650A1 (ja) * 2004-05-24 2008-03-27 日清紡績株式会社 めっきまたは蒸着処理用凹凸粒子
US7163981B2 (en) 2004-08-04 2007-01-16 Toyota Technical Center, U.S.A, Inc. Et Al. Aqueous paint composition and uses thereof
JP2006219731A (ja) 2005-02-10 2006-08-24 Kansai Paint Co Ltd プレコートメタルの裏面用塗料組成物、及びこれを用いたプレコートメタル
KR100650284B1 (ko) * 2005-02-22 2006-11-27 제일모직주식회사 도전성능이 우수한 고분자 수지 미립자, 전도성 미립자 및이를 포함한 이방 전도성 접속재료
RU2456306C1 (ru) * 2005-12-16 2012-07-20 ПиПиДжи ИНДАСТРИЗ ОГАЙО, ИНК. Полиуретаны, изделия и покрытия, изготовленные из них, и способы их производства
JP4962706B2 (ja) * 2006-09-29 2012-06-27 日本化学工業株式会社 導電性粒子およびその製造方法
JP4448511B2 (ja) * 2006-12-26 2010-04-14 株式会社神戸製鋼所 プレコート金属板およびプレコート金属板の製造方法
JP5265215B2 (ja) 2008-02-19 2013-08-14 根上工業株式会社 反応性ポリウレタンビーズ及びその製造方法
JP5430093B2 (ja) * 2008-07-24 2014-02-26 デクセリアルズ株式会社 導電性粒子、異方性導電フィルム、及び接合体、並びに、接続方法
JP5732273B2 (ja) * 2010-03-30 2015-06-10 新日鐵住金ステンレス株式会社 耐プレッシャーマーク性及び耐擦り疵性に優れたクリヤ塗装ステンレス鋼板
JP5819952B2 (ja) 2011-05-26 2015-11-24 株式会社ダイセル ディスプレイ用透明積層フィルム及びその使用方法並びにタッチパネル

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RU2016100421A (ru) 2017-07-18
CN105283519A (zh) 2016-01-27
EP3008145A1 (fr) 2016-04-20
PL3008145T3 (pl) 2017-08-31
JP2015000886A (ja) 2015-01-05
MX2015017010A (es) 2016-04-25
US9738810B2 (en) 2017-08-22
WO2014198452A1 (fr) 2014-12-18
JP6581330B2 (ja) 2019-09-25
EP3008145B8 (fr) 2017-06-07
US20160145461A1 (en) 2016-05-26
CN105283519B (zh) 2018-05-29
CA2910645C (fr) 2021-06-29
RU2655999C2 (ru) 2018-05-30
ES2623278T3 (es) 2017-07-10
ZA201600185B (en) 2017-04-26
CA2910645A1 (fr) 2014-12-18

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